Process for toning tacky image surfaces with dry nonelectroscopic toners

ABSTRACT

Dry nonelectroscopic toners comprising pigmented organic resin particles having a size distribution of 0.2 to 30 micrometers, not more than 50 percent of the particles being less than 1 micrometer surface treated with a combination of at least 1% by weight of an antistatic agent and at least 0.5% of a slip agent as described. The preparation of the toners is described. The toners are useful in color developing positive and negative-working photosensitive elements particularly in an automatic toning machine. Improved clean-up and low stain propensity are achieved.

TECHNICAL FIELD

This invention relates to dry nonelectroscopic toners. More particularlythis invention relates to dry nonelectroscopic toners comprisingpigmented organic resin particles surface treated with an antistaticagent and a slip agent. This invention also relates to the toningprocess using the toners.

BACKGROUND ART

Reproduction processes are known wherein positive-workingphotopolymerizable elements and negative-working photosensitive elementsare exposed imagewise through an original forming nontacky and tackyimage areas. Positive-working photopolymerizable elements are describedin Chu and Cohen U.S. Pat. No. 3,649,268 and negative-workingphotosensitive elements are described in Cohen and Fan U.S. Pat. Nos.4,174,216 and 4,191,572. The image is developed by toning with asuitable toner which desirably adheres only in the tacky image areas.Excess toner which may be present is removed from the nontacky imageareas to provide, for example, an image which is a proof of the originalor which can be used to transfer the image to another surface.Multilayer proofs such as surprint proofs can be made as well.

In view of the increasing importance of proof-making in the printingindustry and the problems inherent therein, improved toners andapplicators for applying these toners are desirable. Some recognizedimprovements in toners are those described in Chu and Manger U.S. Pat.No. 3,620,726, mixtures using these toners described in Gray U.S. Pat.No. 3,909,282 and the toners of Manger, Fickes and Long described inU.S. Pat. No. 4,215,193. From the early use of pads dipped in toners,improved toner applicators are the subject of Sandner U.S. Pat. No.4,019,821 (hand operated toning) and Tobias U.S. Pat. No. 4,069,791(automatic toning). Application of any of the above described toners aswell as known prior art toners to tacky image areas of photosensitiveelements has the problem that the toners are difficult to completelyremove from the nontacky image areas of the said elements. Generally theexcess toner is removed from the nontacky areas by means of mechanicalaction using a cloth, brush or other toner removal means. It is knownthat static is generated by rubbing dissimilar materials together.Depending on the particular film being toned and the toner removalmeans, the amount of static formed varies. For example, cleaning brushesclosest to the film in the triboelectric table would be expected togenerate a relatively low charge. Thus it would be expected that anacrylic brush would generate only a small charge with respect to anelement that contains an acrylic compound in its photosensitive layer.The toner, however, can also generate a charge against the brush (orcleaning means) and the photosensitive element. If the toner, cleaningmeans and element have an identical place in the triboelectric tablesubstantially no static charge would be generated. Such a system, whiledesirable, is not generally achieved. Despite the aforementioneddisadvantage the cleaning of nontacky areas is desirable. In manualapplications this is time consuming. Cleaning operation in a machineincreases the cost thereof. After clean-up, some undesirable stain isusually present.

To overcome the above disadvantages it is desired to provide dry,nonelectroscopic toner particles which, when applied to imagewiseexposed elements containing tacky and nontacky image areas, can beeasily removed from the nontacky areas, e.g., without elaborate clean-upcomponents in automatic toning machines. A further object is to providesuch toners which substantially are nonstaining with respect to thenontacky areas.

DISCLOSURE OF THE INVENTION

In accordance with this invention there is provided a drynonelectroscopic toner comprising pigmented organic resin particleshaving a size distribution within the range of 0.2 to 30 micrometers andnot more than 50 percent of the particles being less than 1 micrometerparticle size, the improvement whereby the pigmented particles aresurface treated with at least 1% by weight of an antistatic agent incombination with at least 0.5% by weight of slip agent selected from theclass consisting of silicone oil having a weight average molecularweight of about 230 to 50,000; saturated hydrocarbons having a weightaverage molecular weight of about 200 to 10,000; and fluorocarboncompounds having a weight average molecular weight of 500 to 500,000.

While not being limited to the following discussion, it is believed thatthe presence of an antistatic agent and a slip agent on the tonersurface act in concert to prevent the toner particles from adhering tonontacky areas. The antistatic agent prevents an electrostatic chargefrom either accumulating or being maintained so that electrostaticattraction between the toners and nontacky areas are minimized orsubstantially eliminated. Simultaneously, working in conjunction withthe antistatic agent, a slip agent prevents the toner particles fromadhering to the nontacky areas by minimizing or preventing frictionalforces or embedding of the particles. The slip agent favors the"skidding" of the toner particles over the nontacky surface andfacilitates their removal while mechanical action, e.g., rubbing, isapplied to the toners to embed them in the tacky image areas. In effect,the two additives working in cooperation substantially improve thedifferentiation of particles between the tacky and nontacky areas of thephotosensitive element. The toners thus adhere to the tacky image areasbut do not adhere to the nontacky areas.

The improved dry toners of this invention are nonelectroscopic tonerscomprising pigmented nonelectroscopic toners comprising pigmentedorganic resin particles having a size distribution within the rangedisclosed above. Nonelectroscopic means that the toners are neitherrepelled from nor attracted to a charged rod when placed in closeproximity to the particles. The lower propensity of the toners to stainnontacky areas and the ease with which the toners can be removed fromsuch areas is largely attributed to the presence on the surface of thetoner particles of the combination of at least 1% by weight of anantistatic agent and at least 0.5% by weight of a slip agent, both ofwhich are more fully described below.

The pigmented organic resin particles are described in Chu and MangerU.S. Pat. No. 3,620,726. Resin matrices include, e.g., polyvinylchloride, cellulose acetate, cellulose acetate butyrate, polystyrene,polymethyl methacrylate. Also useful are water soluble polymer matrices,e.g., polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, theparticular matrix being used depending on the mechanical means ofprocessing the toner down to the desired effective particle sizedistribution. For the purpose of determining whether such a particle hasthe preferred particle size distribution these particles can bemeasured, for example, by a Coulter Counter, Coulter Electronics, Inc.,Hialeah, Fla. The term "particle size" as used herein with respect tothe toners covers the size distribution of the smallest, independentlyacting unit which is called upon to discriminate between the exposed andunexposed areas of the imaging element. The pigmented portion of thetoners, in addition to the pigments illustrated in the examples include:Monastral® Blue G (C.I. Pigment Blue 15), Molybdate Orange (C.I. PigmentRed 104), Toluidine Red YW (C.I. Pigment Red 3)-process aggregatedcrystals, Phthalo Blue (C.I. Pigment Blue 15)-cellulose acetatedispersion, Toluidine Red (C.I. Pigment Red 3), Watchung Red BW (C.I.Pigment Red 48), Toluidine Yellow GW (C.I. Pigment Yellow 1), MonastralBlue BW (C.I. Pigment Blue 15), Monastral Green BW (C.I. Pigment Green7), Pigment Scarlet (C.I. Pigment Red 60), Auric Brown (C.I. PigmentBrown 6), Monastral Green G (Pigment Green 7) and Monastral Maroon B andMonastral Orange, both of which last pigments are sold by themanufacturer under product nos. RT-849-D and YT-756-D, respectively.

Various types of known antistatic agents are useful for treating andcoating the particulate toner surface. Useful antistatic agents includeanionic, cationic, amphoteric and nonionic antistatic agents. Suitableantistatic agents, designated by class type, are as follows:

Anionic

1. Sodium alkyl benzene sulfonate wherein alkyl is an alkyl chain with 8to 18 carbon atoms;

2. Sodium alkyl sulfonate wherein alkyl is an alkyl chain with 10 to 20carbon atoms;

3. Secondary alkyl sulfate wherein one or both alkyl groups aresubstituted with functional groups taken from the group consisting ofester, ether, and alcohol, the alkyl being an alkyl chain of 1 to 18carbon atoms;

4. Phosphorous-containing compounds of the formula (RO)_(m) P(O(OX)_(n)wherein R is an alkyl chain with 4 to 18 carbon atoms, X is an cationtaken from the group consisting of H, K, Na, NH₄, m is 1 or 2 and n is 2or 1; and

5. Amine salt of alkyl sulfate wherein alkyl is an alkyl chain of 8 to18 carbon atoms and amine is taken from the group consisting of ammonia,diethanolamine, triethanolamine and diethylcyclohexyl amine.

Cationic

6. Alkyl trimethyl ammonium bromide wherein alkyl is an alkyl chain with1 to 18 carbon atoms; and

7., 13. Quaternary ammonium compounds of the formula: ##STR1## wherein Rand R₁ may be a saturated or unsaturated alkyl chain with 1 to 24 carbonatoms or mixtures thereof, R₂ may be an alkyl chain of 1 to 24 carbonatoms or R₃ wherein R₃ is a polyether substituent of the formula --(CH₂CH₂ O)_(m) --[CH₂ CH(CH₃)O]_(n) --H wherein m and n may be 0 to 20, thetotal of m and n being at least 1, and X is an anion taken from thegroup consisting of CH₃ SO₄, C₂ H₅ SO₄, (CH₃)₂ PO₄ (C₂ H₅)₂ PO₄ ; thetotal number of carbon atoms in R,R₁ and R₂ should not exceed 38.

Amphoteric

8. Alkyl bis(polyethanoxy)-gamma-sulfopropyl betaine and alkylbis(hydroxyethy)-gamma-sulfopropyl betaine wherein alkyl is an alkylchain with 12 to 24 carbon atoms, and in the former the number ofpolyether units is 1 to 4.

Nonionic

9, 10, 14, 15. Compounds of the formula: R(OCH₂ CH₂)_(n) --OH wherein Ris a saturated and unsaturated alkyl chain with 12 to 18 carbon atoms orCH₃ (CH₂)₇ --CH═CH(CH₂)₈ --, and n is 2 to 10; (Compound 9 is preferred)

11. Compounds of the formula: R(OCH₂ CH₂)_(m) [OCH₂ CH(CH₃)]_(n) --OHwherein R is an alkyl chain with 12 to 18 carbon atoms, m is 0 to 10 andn is 1 to 10.

12. Mono and diglycerides of carboxylic acids having an alkyl chain of12 to 18 carbon atoms.

The specific antistatic agents used in the examples are set forth belowby number which corresponds to the particular definition of theantistatic agents set forth above.

1. Sodium dodecyl benzene sulfonate,

2. Sodium alkyl sulfonate wherein the average number of carbon atoms inthe alkyl chain is 18 (C14 to C22),

3. Sodium salt of acetyloleoyl sulfate,

4. Mono- and bis-alkyl phosphate wherein the alkyl is derived from amixture of C₈, C₁₀ and C₁₂ straight carbon atom chains,

5. Amine salt of lauryl sulfate,

6. Alkyl trimethyl ammonium bromide wherein alkyl chain is derived fromcetyl and lauryl,

7. Quaternary ammonium compound of the formula: ##STR2## wherein R is amixture of cetyl (27%), stearyl (30%) and oleoyl (42%) alkyl chains, R₁is methyl, R₂ and R₃ are polyether substituents of the formula: --(CH₂CH₂ O)_(m) --[CH₂ CH(CH₃)O]_(n) --H wherein m is 1 and n is 3, and X isan anion CH₃ SO₄,

8. Alkyl bis(hydroxyethyl)-gamma-sulfopropyl betaine wherein the alkylchain is of 16 to 18 carbon atoms (C₁₆ to C₁₈),

9. Compound of the formula: R(OCH₂ CH₂)_(n) --OH wherein R is an alkylchain with 12 carbon atoms and n is 4,

10. Compound of the formula: R(OCH₂ CH₂)_(n) --OH wherein R is an alkylchain derived from about 50% lauryl (C₁₂) and cetyl (C₁₆),

11. Compound of the formula: ##STR3##

12. Mono and diglycerides of carboxylic acids having an alkyl chainderived from oleates,

13. Quaternary ammonium compound of the formula ##STR4## wherein R is amixture of saturated and unsaturated C₁₆ to C₁₈ carbon atoms, R₁ ismethyl, R₂ and R₃ are each --(CH₂ CH₂ O)_(m) --H, m is 8 and X is ananion CH₃ SO₄,

14. Compound of the formula:

R--(OCH₂ CH₂)₈.4 --OH wherein R is a mixture of C₁₂, C₁₄ and C₁₆ alkyls,

15. Compound of the formula:

R--(OCH₂ CH₂)₉.9 --OH wherein R is a mixture of saturated andunsaturated C₁₆ to C₁₈ carbon atoms.

Slip agents which are useful for treating and coating the particulatetoner surface in cooperation with the above described antistatic agentsare selected from the group consisting of silicone oil having a weightaverage molecular weight of about 230 to 50,000; saturated hydrocarbonshaving a weight average molecular weight of about 200 to 10,000; andfluorocarbon compounds having a weight average molecular weight of 500to 500,000.

Silicone oils useful in the invention include: polydimethylsiloxane (1)and polymethyl (X) siloxane where X is an alkyl chain with 2 to 12carbon atoms, eg., ethyl to dodecyl.

Saturated hydrocarbons include: motor lubricating oil, SAE 10, (3)paraffin oil viscosity at 55° C. is 70 cps using a Brookfield Viscometermanufactured by Brookfield Engineering Lab, Inc., Stoughton, Mass.;paraffin wax ranging in chain length from 20 to 34 carbon atoms; andpolyethylene waxes having a molecular weight in the range of 1500 to10,000.

Fluorinated hydrocarbons include: fluorocarbon oil (2), e.g., a polymerof (CF₂ CFCl)_(x) wherein X is 6 to 10, average molecular weight 965,viscosity at 38° C. is 2740 cp, viscosity at 71° C. is 160 cp; pourpoint is 21° C., (Fluorolube® Hooker Chemical Co., Niagara Falls, N.Y.),and polytetrafluoroethylene compound (4) from the formula [CF₂ --CF₂]_(x) wherein X is a number of 6 to 10. The above number designationsappear in Example 6.

Silicone oil is the preferred slip agent. The slip agent when a liquidat normal room temperature is a nonsolvent for the toner, isnonvolatile, and is stable to aerial oxidation.

The antistatic agent is present on the surface of the particulate tonerin amounts of at least 1% by weight up to about 12% by weight. Apreferred range for antistatic agent is 5 to 10% by weight. The slipagent is present on said toner surface in an amount of at least 0.5% byweight up to about 12% by weight. A preferred range for the slip agentis 3 to 7% by weight. The above preferred ranges have been foundparticularly effective when applied to tacky image areas using amodified automatic toning apparatus (Tobias U.S. Pat. No. 4,069,791) asdescribed in the examples below. U.S. Pat. No. 4,069,791 is incorporatedherein by reference. If the amount of antistatic and slip agents exceedthe maximum amounts good clean-up is achieved in nontacky image areasbut another problem occurs. It has been found that pick-off of the tonerin the toned image areas occurs. Pick-off is defined as low adhesion ofa toner to tacky areas such that when a photoimagable element is appliedover the toned image it does not adhere well to the previously tonedimage area (so that when the cover sheet of the element is removed areasof the layer above the toned area come off with the cover sheet, takingwith it some of the applied toner).

The toner particles can be readily made as illustrated in the examples.The antistatic agent and slip agent can be added in either order orsimultaneously to the pigmented resin particles. This is generallyaccomplished in a Patterson Kelley Twin Shell Blender manufactured byPatterson Kelley Co., Division of Harsco Corp., East Stroudsburg, Pa. ora Red Devil #30, 5400 Paint Conditioner Model MKI-R, Red Devil, Inc.,Union, N.J. Other comparable milling devices can be used. The milling isfor at least 5 minutes up to 30 minutes or longer. After milling theparticles are permitted to dry or can be dried as is known to thoseskilled in the art.

The static charge on the surface-treated toners of the invention can bedetermined by a test procedure as follows:

50 grams of prepared toner are placed in toner jars and let standovernight in a room at low relative humidity (21%). Twelve 1/4 inchsteel balls are then placed in each jar, and the toners are thoroughlymixed by hand shaking for 60 seconds. After shaking the tops are removedand the voltage is recorded by inserting Sweeney Static Meter No. 1127(contains radioactive material) dated February 1974, B. K. SweeneyManufacturing Co., Denver, Colo. The results achieved with specifiedsilicone-treated cyan toners and Controls C1 and C2 are set forth inTable 1 wherein the percentages are by weight.

                  TABLE 1                                                         ______________________________________                                                        Antistatic   Lubricant                                        Sample Toner    agent; Amt (%)                                                                             (%).sup.3                                                                             Voltage                                  ______________________________________                                        1       C1.sup.1                                                                              None; 0      0       -5,000                                   2       C2.sup.1                                                                              None; 0      4.0     -7,500                                   3      C2       10; 6.5      4.0     -1,250.sup.2                             4      C2       10; 6.5      4.0     -1,250.sup.2                             5      C1        9; 7.0      2.0     0                                        6      C1       10; 2.0      2.0       -700.sup.2                             7      C1        9; 2.0      2.0     -1,100.sup.2                             ______________________________________                                         .sup.1 Controls, see Example 1 for preparation                                .sup.2 Voltages reduced to zero after one minute for Samples 3, 4, 6 and      .sup.3 Lubricant is silicone oil                                         

The toners are useful for color development of a surface havingimagewise tacky and nontacky areas wherein to the image-bearing surfaceis applied the nonelectroscopic toners described above, and the tonerparticles are distributed over the image surface whereby the tonerparticles become embedded solely in the tacky image areas. The remainingtoner particles are physically removed, e.g., by wiping with a suitablecloth or clean-up section of a toning apparatus if one is used. Thenontacky areas are left substantially free of the toner particles. Thetacky surface is present in (a) a photopolymerizable layer(positive-working wherein the exposed areas become photohardened) (Chuet al. U.S. Pat. No. 3,649,268); (b) in an imagewise exposedphotosensitive layer comprising at least one thermoplastic binder and aphotosensitive system, consisting essentially of

I. at least one dihydropyridine compound of the formula ##STR5## whereinR is alkyl, alkenyl of 3 to 11 carbon atoms, phenylalkyl, phenylalkenyl,unsubstituted aryl of 6 to 10 carbon atoms, and heteroaryl,

R₁ and R₂, which can be the same or different, are alkyl, and

R₃ and R₄, which can be the same or different, are COOR', COR', CN, R'is alkyl; and

II. at least one hexaarylbiimidazole compound, (negative-working whereinthe exposed areas are tacky) (Abele et al. U.S. Ser. No. 971,644, filedDec. 21, 1978), or (c) in an imagewise exposed element containingnontonable image areas and tacky nonphotosensitive image areas (alsonegative-working element) (Cohen and Fan U.S. Pat. No. 4,174,216). Thesepatents are incorporated by reference. Other systems known to thoseskilled in the art can be used provided that tacky and nontacky imageareas are formed thereby. The tacky and nontacky image areas in thesesystems can be formed either directly, e.g., by exposure to actinicradiation or by treatment with solutions, heat or other means to obtaintacky image areas.

The above toned elements can be used to form surprint multicolor proofsby laminating at least one other tonable photoimagable layer over thepreviously imagewise toned layer as shown in Example 5 below. Eachtonable layer is exposed through a different color separationtransparency, and the respective layer is colored or developed withtoners in a spectral region corresponding to the color separationtransparency used for exposure. In most cases four photoimaged tonedelements are present in a surprint proof, the toned elements andseparation transparencies corresponding respectively to yellow, magenta,cyan and black.

A particularly preferred process involves automatic color development ofa surface having imagewise tacky and nontacky areas by dispensing andembedding dry particulate toners on the surface by means of an automatictoning apparatus having a dispenser for dispensing said toner above saidsurface, and an applicator for embedding said particulate toners in saidsurface, and means for moving the tacky surface past the dispenser andsaid applicator, the dispenser includes a hopper having an independentlymovable side wall, and means to oscillate the side wall laterally of thetacky surface, thereby to supply the particulate material to the surfaceat a uniform, controlled rate, the improvement wherein the new dry,nonelectroscopic toners described above are automatically dispensed,embedded, and the excess removed (from the nontacky areas).

The toned elements particularly useful in conjunction with the automatictoning apparatus comprise:

1. A supported photopolymer layer having tacky and nontacky areas,solely the tacky image areas being toned with the toners of theinvention, and

2. A photopolymer element comprising in order from top to bottom a layercomprising a nontacky photohardenable material with ethylenicallyunsaturated or benzophenone type groups, a contiguous layer of anonphotosensitive tacky organic material toned imagewise with the tonersof the invention, and a support.

BEST MODE FOR CARRYING OUT THE INVENTION

The best mode for the various types of toners is illustrated in thefollowing examples:

Cyan toner, Example 1, sample 3, for positive-working photopolymerizableelements,

Cyan toner, Example 1, sample 4, for negative-working photosensitiveelements,

Yellow toner, Example 2, samples 11 and 14, for positive-workingphotopolymerizable elements,

Yellow toner, Example 2, samples 2 and 10, for negative-workingphotosensitive elements,

Black toner, Example 3, sample 13, for positive-workingphotopolymerizable elements,

Black toner, Example 3, samples 15 and 17, for negative-workingsensitive elements,

Magenta toner, Example 4, samples 1, 10, and 17, for positive-workingphotopolymerizable elements,

Magenta toner, Example 4, samples 2, 10, 18 and 19, for negative-workingphotosensitive elements.

INDUSTRIAL APPLICABILITY

The dry nonelectroscopic toners are useful for application to positiveor negative-working tacky photosensitive surfaces which are used toprepare color proofs, e.g., overlays and surprints. The toners areparticularly useful in the toning of such elements in conjunction withtoning apparatus, e.g., an automatic toning apparatus described inTobias U.S. Pat. No. 4,069,791, without the need for a cleanup section.The toners are easily prepared and are less susceptible to static chargebuildup than other known nonelectroscopic toners. The toned elementsexhibit good toning and are substantially stain free in the nontackyareas. The clean-up of excess toner is particularly advantageous.

EXAMPLES

The following examples illustrate the invention wherein the parts andpercentages are by weight. The antistatic and slip agents set forth inthe Tables are designated as set forth above. In the Tables below a plusor minus after the sample number indicates a positive-working andnegative-working photosensitive element, respectively.

EXAMPLE 1

The following ingredients are used in the preparation of cyan toners:

    ______________________________________                                        Ingredient           Amount (g)                                               ______________________________________                                        Monastral Blue G (Copper                                                      Phthalocyanine, Pigment Blue 15                                               C.I. No. 74160)      1728.0                                                   Cellulose Acetate    7871.0                                                   Acetone              27,669.6                                                 Water                22,680.0                                                 ______________________________________                                    

The water and acetone are thoroughly mixed and are charged to a Type30-S Attritor stirred ball mill (Union Process Co., Akron, Ohio). Thismill contains 1/8 inch (0.049 cm) Type 440 stainless steel balls thatare agitated at 150 rpm. A nitrogen atmosphere is maintained in the millduring the mixing procedure. Approximately two-third of the weight ofthe cellulose acetate is then added during a 3 to 5 minute period and isagitated in the liquid for about 2 minutes. The pigment is then addedover a 2 minute period followed by the remainder of the celluloseacetate. The mixture is then agitated at about 150 rpm in the mill forabout 6 hours; the mill is drained and washed with water; and thecombined effluents are filtered to collect the wet toner. The wet toneris water-washed and dried in an oven at 115°-125° C., and the driedtoner is pulverized in a hammer mill in combination with dry ice to keepthe pulverized toner flowing through the screens of the hammer mill. Theparticle size distribution of the toner at this point is 0.2 to 30micrometers with not more than 50% of the particles less than 1 micronequivalent spherical diameter.

A portion of the resultant toner is then surface treated by blendingwith dimethylpolysiloxane, 400 g/10 kg of toner (200-Fluid CS, DowCorning Co., Midland, Mich.) in a Patterson-Kelley Twin-Shell blender.

The untreated toner (without silicone treatment) designated Cl, isblended for about 30 minutes with various amounts of the antistaticagents and silicone compound as set forth in Table 2 below. The tonersurface treated with silicone, designated C2, is further blended forabout 30 minutes with various amounts of the antistatic agents also asset forth in Table 2. The blending is accomplished in a Red Devil(#30,5400 Paint Conditioner Model MK1-R manufactured by Red Devil, Inc.,Union, N.J.

A positive-working photopolymerizable element similar to that describedin Example 1, U.S. Pat. No. 3,649,268 is prepared having a 0.0003 inch(0.00076 cm) photopolymer layer coated on 0.0005 inch (0.0013 cm)polyethylene terephthalate film support, and covered by a suitable0.00075 inch (0.0019 cm) polypropylene cover sheet. As described inExample 1 of U.S. Pat. No. 3,649,268, the cover sheet is removed and thephotopolymer layer is laminated to Kromekote paper (on cast coatedside). A suitable solid test pattern image is exposed on thephotopolymer whereby the exposed areas become hardened and the unexposedareas remain tacky. The polyethylene terephthalate film is then removedand the image is developed by toning using the toning apparatusdescribed in Tobias U.S. Pat. No. 4,069,791 wherein the hopper has alaterally oscillating sidewall and the cleaning pad is eliminated.Results are shown in the Table 2 below wherein + means that apositive-working element has been utilized.

A negative-working photosensitive element is prepared by laminating insurface-to-surface relationship at room temperature with a pressure ofabout 40 psi (2.81 kg/dm²) is supported photopolymerizable layer (I) andsupported tonable, tacky elastomer contiguous layer (II). Layers I andII are prepared as follows:

I. Nontonable Photopolymerizable Layer

A coating solution of a photopolymerizable composition is prepared bymixing together the following ingredients:

    ______________________________________                                        Ingredient              Weight (g)                                            ______________________________________                                        Polymethyl methacrylate (MW 200,000-                                                                  41.54                                                 300,000)                                                                      Di-(3-acryloxy-2-hydroxypropyl) ether                                                                 51.86                                                 of Bisphenol-A                                                                (2-Chlorophenyl-4,5-diphenyl imidazolyl)                                                              2.20                                                  dimer                                                                         2-(Stilbyl-4")-(naptho-1',2'; 4,5) 1,2,3-                                                             2.20                                                  triazol-2"-sulfonic acid phenyl ester                                         2-Mercaptobenzoxazole   1.50                                                  Polyethylene oxide (MW 600,000)                                                                       0.70                                                  Methanol                20.70                                                 Methylene chloride      323.70                                                ______________________________________                                    

This solution is coated at a coating weight of about 40 mg/dm² whendried on a clear polyethylene terephthalate film having a thickness of0.0005 inch (0.0015 cm) which is surface treated by electrostaticdischarge at 0.07 coulombs/ft² (0.093 coulombs/m²).

II. Tonable, Tacky Elastomer Contiguous Layer

A coating solution is prepared by mixing together the followingingredients:

    ______________________________________                                        Ingredient            Weight (g)                                              ______________________________________                                        Random copolymer of styrene/                                                                        19.75                                                   butadiene (40/60)                                                             Cis-polybutadiene (Mooney Viscosity                                                                 79.75                                                   55-60)                                                                        Tetra-bis-[methylene 3-(3',5'-di-t-                                                                 0.50                                                    butyl-4'-hydroxyphenyl) proprionate]                                          methane                                                                       Methylene chloride to make                                                                          1333.30                                                 ______________________________________                                    

This solution is coated on polyethylene terephthalate film having areleasable layer of polydimethyl siloxane coated thereon to give acoating weight of about 125 mg/dm² when dried. The negative-workingelement is exposed through the electrostatic discharge treated, clearpolyethylene terephthalate film for about 30 seconds on a Berkey-AscorVacuum Printer exposure device, fitted with a photopolymer lamp (2 KW)and a Kokomo® glass filter (No. 400) Kokomo Opalescent Glass Co.,Kokomo, IN. The distance between the lamp and the vacuum frame of thedevice is about 38 inches (96.52 cm). After exposure, the exposedelement is taped securely to a suitable flat surface, and the clearpolyethylene terephthalate cover sheet is stripped by pulling at onecorner with an even, continuous motion at an angle of about 135°-180°.The resulting exposed, photopolymerized image adheres to the treatedpolyethylene terephthalate film and is removed therewith exposingequivalent areas of the contiguous layer (II). The tacky image isdeveloped by toning using the toning apparatus described above. Resultsare shown in Table 2 below wherein--means that a negative-workingelement has been utilized.

                  TABLE 2                                                         ______________________________________                                                             A-                                                                            mount A-                                                                      of    mount                                                                   Anti- of                                                              Anti-   static                                                                              Sili-                                                    Ton-   static  Agent cone  Clean-                                                                              Stain-                                                                              Toning                           Sample                                                                              er     Agent   (%)   (%)   up    Free  Quality                          ______________________________________                                        1+    C1     10      7.5   0     Excel-                                                                              Poor  Poor                                                              lent                                         2+    C2     None    0     4.0   Poor  Good  Good                             3± C1     10      7.5   2.0   Excel-                                                                              Good  Good                                                              lent                                         4± C2     10      7.5   4.0   Excel-                                                                              Good  Good                                                              lent                                         5± C1     10      7.5   1.0   Excel-                                                                              Good  Good                                                              lent                                         6± C1      9      7.0   2.0   Good  Good  Good                             7± C1      7      6.0   4.0   Good  Good  Good                             8± C1     13      7.5   4.0   Good  Good  Good                             9± C1     11      6.0   4.0   Excel-                                                                              Good  Good                                                              lent                                         10±                                                                              C1     7 and   6.0 and                                                                             4.0   Good  Good  Good                                          10      6.0                                                      11±                                                                              C1     14       6.0  4.0   Good  Good  Good                             12±.sup.1                                                                        C1     10      1.5   1.5   Good  Good  Good                             ______________________________________                                         .sup.1 The tacky image areas are developed by hand toning using the tonin     applicator as described in Sandner, U.S. Pat. No. 4,019,821.             

EXAMPLE 2

The following ingredients are used to prepare yellow toners:

    ______________________________________                                        Ingredient           Amount (g)                                               ______________________________________                                        Dalamar yellow (Pigment                                                                            4,360.0                                                  Yellow 74, C.I. No. 11741)                                                    Cellulose acetate    6,538.0                                                  Acetone              27,669.6                                                 Water                22,680.6                                                 Dimethylpolysiloxane described                                                                     1,150.0.sup.1                                            in Example 1                                                                  ______________________________________                                         .sup.1 Based on 10 kg of toner                                           

The toner is prepared as described in Example 1 except that the millingtime is 4 hours. The toner is dried and pulverized (designated Y1). Aportion of Y1 toner is surface treated with dimethylpolysiloxane asdescribed in Example 1 (designated Y2). The two toners are mixed withvarying amounts of the antistatic agents set forth in Table 3 below. Insome samples additional silicone is mixed with the toners. Positive andnegative-working elements as described in Example 1 are developed usingthe toning apparatus described in Example 1 except for Samples 15 and 16as noted.

                  TABLE 3                                                         ______________________________________                                                             A-                                                                            mount A-                                                                      of    mount                                                                   Anti- of                                                              Anti-   static                                                                              Sili-                                                    Ton-   static  Agent cone  Clean-                                                                              Stain-                                                                              Toning                           Sample                                                                              er     Agent   (%)   (%)   up    Free  Quality                          ______________________________________                                        1± Y1     10      5.0   10.0  Good  Good  Good                             2± Y1     10      10.0  10.0  Good  Good  Good                             3± Y1     7 and   4.0 and                                                                             10.0  Good  Good  Good                                          10      4.0                                                      4± Y2      7      7.5   10.0  Good  Good  Good                             5± Y2     11      6.0   10.0  Excel-                                                                              Good  Excel-                                                            lent        lent                             6± Y2     12      5.0   10.0  Fair  Good  Good                             7± Y2      7      6.0   10.0  Good  Good  Good                             8± Y2     14      6.0   10.0  Good  Good  Good                             9± Y2     10      7.5   10.0  Good  Good  Good                             10±                                                                              Y2     10      9.8   10.0  Good  Good  Good                             11±                                                                              Y1     10      9.8   5.0   Good  Good  Good                             12.sup.a ±                                                                       Y1     10      10.0  0     Good  Poor  Good                             13.sup.a ±                                                                       Y1       9     10.0  0     Good  Poor  Good                             14±                                                                              Y1     10      7.5   5.0   Good  Good  Good                             15.sup.b ±                                                                       Y1     10      4.0   6.0   Good  Good  Good                             16.sup.b ±                                                                       Y1     10      4.0   8.0   Good  Good  Good                             17±                                                                              Y1      9      9.5   5.0   Good  Good  Good                             18.sup.a ±                                                                       Y2     None    0     10.0  Poor  Good  Good                             ______________________________________                                         .sup.a Controls                                                               .sup.b Developed by hand toning as described in Table 2, Example 1       

EXAMPLE 3

The following ingredients are used to prepare black toners:

    ______________________________________                                        Ingredient           Amount (g)                                               ______________________________________                                        Carbon Black, Sterling                                                                             6,300.0                                                  NS N 774 (Pigment Black 7,                                                    C.I. No. 77266)                                                               Cellulose acetate    6,300.0                                                  Acetone              27,669.6                                                 Water                22,680.0                                                 Dimethylpolysiloxane described                                                                     970.0.sup.1                                              in Example 1                                                                  ______________________________________                                         .sup.1 Based on 12.6 kg of toner                                         

The toner is prepared in the same manner as described in Example 1.

The dry toner is pulverized (designated B1). A portion of B1 toner issurface treated with dimethylpolysiloxane as described in Example 1(designated B2). The two toners are mixed with varying amounts of theantistatic agents set forth in Table 4 below. In some samples additionalsilicone is mixed with the toners. Positive and negative-workingelements as described in Example 1 are developed using the toningapparatus described in Example 1 except for Sample 16 as noted.

                  TABLE 4                                                         ______________________________________                                                             A-                                                                            mount A-                                                                      of    mount                                                                   Anti- of                                                              Anti-   static                                                                              Sili-                                                    Ton-   static  Agent cone  Clean-                                                                              Stain-                                                                              Toning                           Sample                                                                              er     Agent   (%)   (%)   up    Free  Quality                          ______________________________________                                        1± B1     7 and   4.0 and                                                                             8.0   Good  Good  Good                                          10      4.0                                                       2.sup.a ±                                                                       B2     None    0     8.0   Poor  Good  Good                             3± B2      7      6.0   8.0   Good  Good  Good                             4± B2     12      6.0   8.0   Good  Good  Good                             5± B2     14      6.0   8.0   Good  Good  Good                             6± B2     10      6.0   8.0   Good  Good  Good                             7± B2      7      7.5   8.0   Good  Good  Good                             8± B2     10      7.5   8.0   Good  Good  Good                              9.sup.a ±                                                                       B1      9      10.0  0     Good  Mod-  Good                                                                    erate                                  10±                                                                              B2     10      9.5   8.0   Good  Good  Good                             11.sup.a +                                                                          B2     None    0     10.0  Poor  Good  Good                             12+   B1      9      5.0   10.0  Good  Good  Good                             13+   B1      9      10.0  4.0   Good  Good  Good                             14+   B1     10      9.5   4.0   Good  Good  Good                             15-   B2      9      2.0   8.0   Good  Good  Good                             16.sup.b -                                                                          B2      9      2.0   2.0   Good  Good  Good                             17-   B2      9      2.0   10.0  Good  Good  Good                             ______________________________________                                         .sup.a Controls                                                               .sup.b Developed by hand toning as described in Table 2, Example 1       

EXAMPLE 4

The following ingredients are used to prepare magenta toners.

    ______________________________________                                        Ingredient       M.sub.1  M.sub.2  M.sub.3                                    ______________________________________                                        Quindo Magenta   5,312.0  3,910.0  3,315.0                                    (Pigment Red 122,                                                             Allied Chemical Corp.,                                                        Harmon Colors)                                                                Indo Brilliant Scarlet                                                                         --       730.0    1,560.0                                    Toner (Pigment Red                                                            123, C.I. No. 71145)                                                          Cellulose acetate                                                                              6,469.0  6,960.0  6,929.0                                    Acetone          22,669.6 27,669.6 27,669.6                                   Water            22,669.6 22,680.0 22,680.0                                   Dimethylpolysiloxane                                                                           679.0.sup.1                                                                            679.0.sup.1                                                                            679.0.sup.1                                described in Example 1,                                                       ______________________________________                                         .sup.1 Based on 11.8 kg of toner                                         

The toners are prepared in the same manner described in Example 1. Afterdrying the toners are pulverized (designated M1, M2 and M3). A portionof each toner is surface treated with dimethylpolysiloxane as describedin Example 1 (designated M4, M5 and M6). The toners are mixed withvarying amounts of the antistatic agents as listed in Table 5 below. Insome samples additional silicone is mixed with the toners. Positive andnegative-working elements as described in Example 1 are developed usingthe toning apparatus described in Example 1 except for Samples 21 to 25as noted.

                  TABLE 5                                                         ______________________________________                                                             A-                                                                            mount A-                                                                      of    mount                                                                   Anti- of                                                              Anti-   static                                                                              Sili-                                              Sam-         static  Agent cone  Clean-                                                                              Stain-                                                                              Toning                           ple  Toner   Agent   (%)   (%)   up    Free  Quality                          ______________________________________                                         1±                                                                             M2      10      10.0  4.0   Good  Good  Good                              2±                                                                             M2      10      10.0  8.0   Good  Good  Good                              3±                                                                             M1      10 and  5.0 and                                                                             6.0   Good  Good  Good                                          7       5.0                                                       4±                                                                             M4      12      6.0   6.0   Fair  Good  Good                              5.sup.a ±                                                                      M4      None    0     9.0   Poor  Good  Good                              6.sup.a ±                                                                      M5      None    0     9.0   Poor  Good  Good                              7.sup.a ±                                                                      M6      None    0     9.0   Poor  Good  Good                              8±                                                                             M4      11      7.5   6.0   Good  Good  Good                              9±                                                                             M4      10      7.5   6.0   Good  Good  Good                             10±                                                                             M4      10      9.0   6.0   Good  Good  Good                             11±                                                                             M4       7      9.0   6.0   Good  Good  Good                             12±                                                                             M4      10      7.5   9.0   Good  Good  Good                             13.sup.a ±                                                                      M1      10      10.0  0     Good  Mod-  Good                                                                    erate                                  13.sup.a -                                                                         M1      10      10.0  0     Good  Poor  Good                             14.sup.a +                                                                         M2      10      10.0  0     Good  Mod-  Good                                                                    erate                                  14.sup.a -                                                                         M2      10      10.0  0     Good  Poor  Good                             15±                                                                             M5      10      7.0   9.0   Good  Good  Good                             16.sup.a +                                                                         M2       9      10.0  0     Excel-                                                                              Poor  Good                                                              lent                                         16.sup.a -                                                                         M2       9      10.0  0     Fair  Poor  Good                             17±                                                                             M2      10      8.0   4.0   Good  Good  Good                             18±                                                                             M2      10      8.0   8.0   Good  Good  Good                             19±                                                                             M3      10      8.0   8.0   Good  Good  Good                             20±                                                                             M3      10      8.0   4.0   Good  Good  Good                             21.sup.b ±                                                                      M3      10      4.0   4.0   Good  Good  Good                             22.sup.b ±                                                                      M3      10      4.0   6.0   Good  Good  Good                             23.sup.b ±                                                                      M1      10      4.0   6.0   Good  Good  Good                             24.sup.b ±                                                                      M1      10      3.0   3.0   Good  Good  Good                             25.sup.b ±                                                                      M3      10      3.0   3.0   Good  Good  Good                             26.sup.a ±                                                                      M3      None    0     6.4   Poor  Good  Good                             27+  M1       9      8.5   3.0   Good  Good  Good                             28±                                                                             M2      10      9.0 and                                                                             4.0 and                                                                             Good  Good  Good                                  (73%)           4.0   6.0                                                     and                                                                           M5                                                                            (27%)                                                                    ______________________________________                                         .sup.a Control                                                                .sup.b Developed by hand toning as described in Table 2, Example 1       

EXAMPLE 5

A photopolymerizable composition is prepared by mixing together thefollowing ingredients:

    ______________________________________                                        Ingredient            Amount (parts)                                          ______________________________________                                        Polymethylmethacrylate,                                                       molecular weight 30,000,                                                      density 1.13 g/cc     32.40                                                   Trimethylolpropane trimethacrylate                                                                  35.60                                                   2-o-Chlorophenyl-4,5-bis-(m-methoxy-                                          phenyl)imidazolyl dimer                                                                             1.58                                                    2-Mercaptobenzothiazole                                                                             0.79                                                    Polyoxyethylene lauryl ether                                                                        7.90                                                    ______________________________________                                    

The mixture is dissolved in methylene chloride (20% solution) and iscoated onto a 0.001 inch (0.0025 cm) thick polyethylene terephthalatesupport and a 0.001 inch (0.0025 cm) thick cover sheet of polypropyleneis laminated onto the coating at room temperature. The cover sheet isremoved at room temperature with substantially no effect on thephotopolymerizable layer, and the layer is laminated at about 110° C. tothe smooth side of Kromekote® cast-coated one-side paper, manufacturedby Champion Paper and Fiber Company on a fixed-bed transfer machine asdescribed in Chu et al. U.S. Pat. No. 3,594,535, incorporated byreference. The photopolymer layer is exposed at a distance of about 27inches (68.6 cm) through a minus-blue separation halftone positive forabout 8 seconds using a nuArc® Plate Maker "Flip Top", Model FT26M-2carbon arc light source. The polyethylene terephthalate support isremoved at room temperature and yellow toner (Y1), prepared as describedin Example 2 containing 10% antistatic agent, 10, and 5% silicone, isapplied to the exposed photopolymer surface using the automatic tonerapparatus described in Example 1, adapted for 4-toner application. Theclean-up and toning quality are good and the stain-free quality is alsogood. The toner adheres only to those image areas that were not exposedto the radiation.

The cover sheet is removed from a second element coated with theabove-described composition, and the clear photopolymer layer islaminated onto the yellow-toned layer, obtained above, at a temperatureof 110° C. The two-layer element is exposed through a minus-greenseparation halftone positive for 3 seconds using the nuArc® lightsource. The base support is stripped from the photopolymer, and amagenta toner (M1) prepared as described in Example 4 containing 10%antistatic agent, 10, and 4% silicone, is applied to the exposedphotopolymer surface at room temperature using the automatic toningapparatus described above. The clean-up, toning quality and stain-freequality are good.

The cover sheet is removed from a third photopolymerizable elementcoated with the above-described composition and the clear photopolymerlayer is laminated onto the magenta-toned layer, obtained above, at atemperature of 110° C. This is exposed through the minus-red halftonepositive for 3 seconds using the nuArc® light source. The polyethyleneterephthalate support is removed from the layer, and a cyan toner (C1)prepared as described in Example 1 containing 8% antistatic agent, 10,and 2% silicone, is applied to the exposed photopolymer surface usingthe automatic toner apparatus described above. The clean-up, toningquality and stain-free quality are good.

A fourth photopolymerizable layer is laminated onto the cyan-toned layerof the three-layer film base using the same procedure and under the sameconditions used in preparing the two previous layers. The fourth layeris exposed through a black printer halftone positive for 3 seconds usingthe nuArc light source. After stripping off the polyethyleneterephthalate support, a black toner (B1) prepared as described inExample 3 containing 10% antistatic agent, 10, and 4% silicone, isapplied to the exposed photopolymer surface using the automatic tonerapparatus described above. The clean-up, toning quality and stain-freequality are good.

After application of the black toner, a fifth layer of photopolymer islaminated at 110° C. over the four-color halftone positive whichsimulates closely a press proof.

The above procedure was repeated except that the toners used werecontrol toners containing silicone but no antistatic agent as follows:

Yellow toner (Y2), 10% silicone

Magenta toner (M4), 9% silicone

Cyan toner (C2), 4% silicone

Black toner (B2), 8% silicone

The stain-free quality and toning quality are good but the clean-upquality of the exposed areas of the photopolymer layers is poor.

EXAMPLE 6

Positive-working photopolymerizable elements are prepared as describedin Example 5 and are imagewise exposed as described in that example. Acyan toner (C1) is blended as described in Example 1 with thepercentages of antistatic agent and slip agent as set forth in Table 6below. The slip agents are designated by number as set forth above. Thestain optical densities are measured on a Cary recordingspectrophotometer.

                  TABLE 6                                                         ______________________________________                                                       Amount of         Amount of                                          Antistatic                                                                             Antistatic        Slip Agent                                                                            Stain                                Sample                                                                              Agent    Agent (%) Slip Agent                                                                            (%)     (O.D.)                               ______________________________________                                        1     None     0         None    0       0.05                                 2     10       1.0       None    0       0.04                                 3     None     0         1       0.5     0.025                                4     10       1.0       1       0.5     0.01                                 5     None     0         2       0.5     0.04                                 6     None     0         2       2.0     0.03                                 7     10       6.0       2       4.0     0.01                                 8     10       6.0       2       0.5     0.02                                 9     None     0         3       0.5     0.045                                10    None     0         3       2.0     0.03                                 11    10       6.0       3       4.0     0.005                                12    10       6.0       3       0.5     0.02                                 13    None     0         4       2.5     0.02                                 14    10       6.0       None    0       0.03                                 15    10       6.0       4       0.5     0.015                                ______________________________________                                    

I claim:
 1. A process for color development of a surface havingimagewise tacky and nontacky areas which comprises(a) applying to theimage-bearing surface dry nonelectroscopic toner comprising pigmentedorganic resin particles having a size distribution within the range of0.2 to 30 micrometers and not more than 50 percent of the particlesbeing less than 1 micrometer particle size, the improvement whereby thepigmented particles are surface coated with at least 1% by weight of anantistatic agent in combination with at least 0.5% by weight of slipagent selected from the class consisting of silicone oil having a weightaverage molecular weight of about 230 to 50,000; saturated hydrocarbonshaving a weight average molecular weight of about 200 to 10,000; andfluorocarbon compounds having a weight average molecular weight of 500to 500,000 and (b) distributing the toner particles over the imagesurface whereby the distributed toner particles become embedded solelyin the tacky image areas, and (c) physically removing toner particlesfrom the nontacky areas which are left substantially free of the tonerparticles.
 2. A process according to claim 1 wherein the tacky surfaceis present in a photopolymerizable layer.
 3. A process according toclaim 1 wherein the tacky surface is present in an imagewise exposedphotosensitive layer comprising at least one thermoplastic binder and aphotosensitive system, consisting essentially ofI. at least onedihydropyridine compound of the formula ##STR6## wherein R is alkyl,alkenyl of 3 to 11 carbon atoms, phenylalkyl, phenylalkenyl,unsubstituted aryl of 6 to 10 carbon atoms, and heteroaryl,R₁ and R₂,which can be the same or different, are alkyl, and R₃ and R₄, which canbe the same or different, are COOR', COR', CN, R' is alkyl; and II. atleast one hexaarylbiimidazole compound.
 4. A process according to claim1 wherein the tacky surface is present in an imagewise exposed elementconsisting nontonable image areas and tacky nonphotosensitive imageareas.
 5. A process according to claim 1 wherein a surprint multicolorproof is formed by laminating at least one other tonable photoimagablelayer over the previously imagewise toned layer, each tonablephotoimagable layer being exposed through a different color separationtransparency and the respective layer having been colored with toners ina spectral region corresponding to the color separation transparencyused for exposure.
 6. A process according to claim 5 wherein fourphotoimaged toned elements are present in the surprint multicolor proofand the toned element and separation transparencies correspond,respectively, to yellow, magenta, cyan and black.
 7. A process accordingto claim 1 wherein the slip agent on the toner surface ispolydimethylsiloxane or polymethyl(X)siloxane where X is an alkyl chainwith 2 to 12 carbon atoms.
 8. A process according to claim 1 wherein theantistatic agent on the toner surface is an anionic antistatic agent. 9.A process according to claim 8 wherein the anionic antistatic agent is amember taken from the group consisting of:(a) sodium alkyl benzenesulfonate wherein alkyl is an alkyl chain with 8 to 18 carbon atoms; (b)sodium alkyl sulfonate wherein alkyl is an alkyl chain with 10 to 20carbon atoms; (c) secondary alkyl sulfate wherein one or both alkylgroups are substituted with functional groups taken from the groupconsisting of ester, ether, and alcohol, the alkyl being an alkyl chainof 1 to 18 carbon atoms; (d) phosphorous-containing compound of theformula (RO)_(m) P(O(OX)_(n) wherein R is an alkyl chain with 4 to 18carbon atoms, X is an cation taken from the group consisting of H, K,Na, NH₄, m is 1 or 2 and n is 2 or 1; and (e) amine salt of alkylsulfate wherein alkyl is an alkyl chain of 8 to 18 carbon atoms andamine is taken from the group consisting of ammonia, diethyanolamine,triethanolamine and diethylcyclohexyl amine.
 10. A process according toclaim 1 wherein the antistatic agent on the toner surface is a cationicantistatic agent.
 11. A process according to claim 10 wherein thecationic antistatic agent is a member taken from the group consisting of(a) alkyl trimethyl ammonium bromide wherein alkyl is an alkyl chainwith 1 to 18 carbon atoms; and(b) Quaternary ammonium compounds of theformula: ##STR7## wherein R and R₁ may be a saturated or unsaturatedalkyl chain with 1 to 24 carbon atoms or mixtures thereof, R₂ may be analkyl chain of 1 to 24 carbon atoms or R₃ wherein R₃ is a polyethersubstituent of the formula --(CH₂ CH₂ O)_(m) --[CH₂ CH(CH₃)O]_(n) --Hwherein m and n may be 0 to 20, the total of m and n being at least 1,and X is an anion taken from the group consisting of CH₃ SO₄, C₂ H₅ SO₄,(CH₃)₂ PO₄, (C₂ H₅)₂ PO₄ ; the total number of carbon atoms in R,R₁ andR₂ should not exceed
 38. 12. A process according to claim 1 wherein theantistatic agent on the toner surface is an amphoteric antistatic agent.13. A process according to claim 12 wherein the amphoteric antistaticagent is taken from the class consisting of alkylbis(polyethanoxy)-gamma-sulfopropyl betaine and alkylbis(hydroxyethyl)-gamma-sulfopropyl betaine wherein alkyl is an alkylchain with 12 to 14 carbon atoms and in the former the number ofpolyether units is 1 to
 4. 14. A process according to claim 1 whereinthe antistatic agent is a nonionic antistatic agent.
 15. A processaccording to claim 14 wherein the nonionic antistatic agent is a membertaken from the group consisting of a compound of the formula:(a) R(OCH₂CH₂)_(n) --OH wherein R is a saturated and unsaturated alkyl chain with12 to 18 carbon atoms or CH₃ (CH₂)₇ --CH═CH(CH₂)₈ --, and n is 2 to 10;(b) R(OCH₂ CH₂)_(m) [OCH₂ CH(CH₃)]_(n) --OH wherein R is an alkyl chainwith 12 to 18 carbon atoms, m is 0 to 10 and n is 1 to 10; and (c) monoand diglycerides of carboxylic acids having an alkyl chain of 12 to 18carbon atoms.
 16. A process according to claim 1 wherein the pigmentedresin particles are comprised of cellulose acetate particles havingpigment particles embedded in their surfaces.
 17. A process forautomatic color development of a surface having imagewise tacky andnontacky areas by dispensing and embedding dry particulate toners on thesurface by means of an automatic toning apparatus having a dispenser fordispensing said toner above said surface, and an applicator forembedding said particulate toners in said surface, and means for movingthe tacky surface past the dispenser and said applicator, the dispenserincludes a hopper having an independently movable side wall, and meansto oscillate the side wall laterally of the tacky surface, thereby tosupply the particulate material to the surface at a uniform, controlledrate, the improvement wherein dry, nonelectroscopic toners comprisingpigmented organic resin particles having a size distribution within therange of 0.2 to 30 micrometers and not more than 50 percent of theparticles being less than 1 micrometer particle size are surface coatedwith at least 1% by weight of an antistatic agent in combination with atleast 0.5% by weight of slip agent selected from the class consisting ofsilicone oil having a weight average molecular weight of about 230 to50,000; saturated hydrocarbons having a weight average molecular weightof about 200 to 10,000; and fluorocarbon compounds having a weightaverage molecular weight of 500 to 500,000 are automatically dispensed,embedded, and the excess removed.
 18. A process according to claim 17wherein the tacky surface is present in a photopolymerizable layer. 19.A process according to claim 17 wherein the tacky surface is present inan imagewise exposed photosensitive layer comprising at least onethermoplastic binder and a photosensitive system, consisting essentiallyofI. at least one dihydropyridine compound of the formula ##STR8##wherein R is alkyl, alkenyl of 3 to 11 carbon atoms, phenylalkyl,phenylalkenyl, unsubstituted aryl of 6 to 10 carbon atoms, andheteroaryl,R₁ and R₂, which can be the same or different, are alkyl, andR₃ and R₄, which can be the same or different, are COOR', COR', CN, R'is alkyl; and II. at least one hexaarylbiimidazole compound.
 20. Aprocess according to claim 17 wherein the tacky surface is present in animagewise exposed element containing nontonable image areas and tackynonphotosensitive image areas.